US4428863A - Alumina compositions of improved strength useful as catalyst supports - Google Patents
Alumina compositions of improved strength useful as catalyst supports Download PDFInfo
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- US4428863A US4428863A US06/395,560 US39556082A US4428863A US 4428863 A US4428863 A US 4428863A US 39556082 A US39556082 A US 39556082A US 4428863 A US4428863 A US 4428863A
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- barium
- alumina
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/005—Spinels
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/66—Silver or gold
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/04—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen
- C07D301/08—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen in the gaseous phase
- C07D301/10—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen in the gaseous phase with catalysts containing silver or gold
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
Definitions
- Aluminas and alumina-silicates are well known to be useful as catalysts, adsorbents and catalyst supports. These materials are made by fusing high purity (99+%) aluminum oxide with or without silica (usually as sodium silicate). They may be very porous or non-porous and have a high or low surface area depending upon the use to be made of them. When used as a catalyst the support may comprise any porous, inert material which does not detrimentally influence the catalytic reaction wherein it is employed.
- An early patent describing a method of making a pelleted alumina catalyst is U.S. Pat. No. 2,499,675.
- the particular support therein is said to be useful as a support for a silver catalyst employed in the oxidation of ethylene to ethylene oxide.
- the support material comprises 90 percent or more by weight alpha alumina and 1 to 6 percent by weight silica.
- a preferred support material comprises 90 percent or more by weight alpha alumina, 1 to 6 percent by weight silica and 0.1 to 0.4 percent by weight baryta.
- the high-purity aluminum oxide preferably in the alpha alumina phase is throughly mixed with temporary and permanent binders.
- the temporary binders are thermally decomposable organic compounds of moderate to high molecular weight (i.e., molecular weights above about 250) and, on decomposition, produce the pore structure of the support.
- the permanent binders are inorganic clay-type materials having fusion temperatures below that of the alumina and are responsible for imparting mechanical strength to the finished support. Silica and baryta can also be added in quantity sufficient to obtain a finished support of the desired composition. After thorough dry-mixing, sufficient water is added to the mass to form the mass into a paste-like substance.
- the catalyst support particles are then formed from the paste by conventional means such as, for example, high pressure extrusion, granulation or other ceramic forming processes.
- the particles are then dried and are subsequently fired at an elevated temperature which is in the range of 1,200° to 1,600° C.
- the temporary binders are thermally decomposed to carbon dioxide and water and are volatilized, leaving voids in the support mass. These voids are the genesis of the pore structure of the finished support.
- Suitable temporary binders include such materials as the celluloses and substituted celluloses, e.g. cellulose itself, methylcellulose, ethylcellulose, and carboxyethylcellulose, stearates such as organic stearate esters, e.g. methyl or ethyl stearate, waxes and the like.
- the temperature reaches the point at which the permanent binder (inorganic clay such as the kaolins or the ball clays) fuses.
- the catalyst support is then permitted to cool and, during cooling, the permanent binder sets and acts as a cement to bond the catalyst support particles and thereby impart mechanical strength to the support and ensure maintenance of the pore structure.
- Catalyst supports of desired characteristics can be readily produced by the foregoing procedure. Control of pore size, pore size distribution and porosity are readily affected by appropriate adjustment in known manner of the size of the starting alumina particles, and of the particle size and concentration of the temporary and of the permanent binders in the starting mix. The larger the starting alumina particle size, the greater will be the porosity of the finished catalyst. The more homogeneous in size are the alumina particles, the more uniform will be the pore structure. Similarly, increasing the concentration of the temporary binder will also increase the overall porosity of the finished catalyst support.
- High purity alumina is desired in order to avoid any extraneous elements, e.g. sodium, which might deleteriously affect the catalytic coating. This is especially true for those supports used to make silver catalysts for use in making ethylene oxide. Such high purity supports have been made, but most do not have as good crush strength as do the lower purity supports. Those high strength, high purity supports which have been made have low porosity which is undesirable in supports for use in EO manufacture. Supports used for silver catalysts employed in the oxidation of ethylene to ethylene oxide also are desirably of low surface area, i.e. less than about 1 m 2 /g. It would, therefore, be highly desirable to have high purity, high porosity, low surface area supports of increased strength for use in making silver catalysts for EO manufacture.
- the present invention is the discovery that adding to the high purity alumina particular barium salts, i.e. the aluminate or silicate, shows an unexpected improvement in strength and abrasion resistance over the known manner of adding barium which is as the oxide, i.e. baryta, as indicated above.
- barium aluminate previously has not been disclosed.
- Barium aluminate and barium silicate each provide improved crush strength and abrasion resistance to the support when incorporated into the alumina as binders in making a high purity low surface area alumina binders in making a high purity low surface area alumina support. Sufficient of the barium compound is added to provide from about 0.1% to about 1.0% barium in the finished support.
- the high purity alumina support of the present invention which is useful as a carrier for silver is made from a high purity ⁇ -alumina 99.5% by weight Al 2 O 3 containing about 0.08% SiO 2 , about 0.04% Fe 2 O 3 and about 0.2% volatile components. Water content can be up to 0.3%. While the above analysis of the high purity alumina is representative, the purity of the alumina may vary from about 98.9% to about 99.9% providing certain impurities, namely Na 2 O, SiO 2 and Fe 2 O 3 are kept below about 0.6, 0.2 and 0.05%, respectively.
- alumina is added from about 0.19% to about 1.9% of barium aluminate or from about 0.16% to about 1.6% of barium silicate, based on the total weight of alumina and barium compound together, with sufficient water to make a paste which can be molded or shaped into pellets or spheres.
- water is added in an amount of from about 8% to about 30% by weight based on the total weight of dry components, including additives, such as pore forming materials.
- additives e.g. an alkylated cellulose
- Such materials are methylcellulose, ethylcellulose, hydroxypropylmethylcellulose, hydroxybutylmethylcellulose, and the like.
- Other pore forming agents which can be substituted for the cellulosic materials are polyvinylalcohol, polyglycols, starches, gelatins, graphite, cereal grains, flour, plastics, e.g. polyethylene, organic ion exchange resins, and natural and synthetic fibers, e.g. cotton and polyester. They are added in amounts of from about 2% to about 20%. Since the barium aluminate and silicate act as binders for the alumina, no additional binders or cements ordinarily used by the art are necessary.
- the paste-like material having been formed into pellets or spheres, is fired at temperatures of from about 1200° C. to about 1700° C. for a period of time from about 0.5 to about 24 hours, the firing being done in an oxygen or air atmosphere.
- the temperature of firing is sufficiently high to fuse the alumina and barium salts without the addition of other binders normally used for that purpose. If desired, however, other known binders may be added providing no deleterious effect is obtained.
- barium is usually added to the silver coating, either concurrently with the silver salt or prior or post added as a water soluble salt in order to prevent sintering of the silver during use. It was determined, however, that additional barium was not needed on the surface of the support in order to prevent the sintering of the silver coating.
- barium oxide is known to have little anti-sintering effect when used as a component of the support, it was surprising to observe this effect when the barium was added as either the aluminate or silicate according to the present invention. In fact, it was even more surprising to find that, when the support material had barium incorporated according to the present invention, additional barium co-deposited on the surface of the support with the silver, e.g. as nitrate, usually had a deleterious effect on the activity and/or selectivity when used in the oxidation of ethylene to EO.
- a series of carriers was prepared from 325 mesh alumina powder. Typical composition for this alumina is 99.5 weight percent Al 2 O 3 , 0.10 weight percent Na 2 O, 0.08 weight percent SiO 2 , 0.04 weight percent Fe 2 O 3 , and 0.20 weight percent other volatiles. Total water content may be up to 0.3 weight percent.
- the apparatus used for evaluating attrition on these small laboratory carrier preparations was constructed to specifically determine abrasion loss on very small amounts of material.
- the container for the test was a fibreboard tube with a metal bottom and screw-on metal cap.
- the outside height was 53/4 inch. Outside diameter was 23/8 inch.
- a 1/16 inch thick silicon rubber pad was placed in the lid top and container bottom to completely cover the surfaces.
- the inside diameter of the tube was 21/8 inch.
- the tube surface was covered with a ribbed rubber liner measuring 65/8 inch by 55/8 inch. Ribs of the rubber liner were made to run parallel to the tube axis. The end liners are glued into place but the ribbed liner is compressed in place without glue.
- Trimming of the inner liner was performed to make the edges fit flush on the end liners.
- the ribs of the inner liner were on 1/4 inch centers and measured 3/32 inch at the base. Total rib height off the tube surface was 0.135 inch with the valley between the ribs 0.096 inch off the tube surface.
- Two strips of silicone rubber measuring 77/8 inch by one inch by 1/8 inch were mounted on the outside ends of the tube for a roll surface.
- the container was rolled on a Norton Company roller mill to produce attrition which was measured at 5 minute intervals up to a total time of 1/2 hour. The procedure was to place 65 grams of carrier in the container and rotate the tube at 208 revolutions per minute and weigh the dust which fell through a 12 mesh screen each 5 minutes. Attrition was expressed as accumulative weight percent based on the original charge weight.
- Crush strength was determined by testing at 0.5 inch per minute loading rate on a Comten Industries crush strength tester, Model No. 922-MV-05-OP. Median pore size and porosity determination were made by standard analysis on a Micrometrics porosimeter employing mercury intrusion.
- the alumina powder was mixed with the additives employed and deionized water and thoroughly blended on a roller mill for 1/2 hour to obtain a uniform mixture. Spheres having a diameter of 1/4 inch were then formed from the pasty mass, after which they were heated to 1500° C. for 10 hours. On cooling each batch was tested for physical properties and also compared with a similar batch (N) of a commercially prepared support without the barium aluminate.
- Table I shows the amounts and kinds of additives used and Table II the resulting properties.
- All the above support materials had surface area of between about 0.30 and 0.35 m 2 /g. It should be noted that all batches showed crush strength improvement with increased temperature and/or time while crush strengths at all firing temperatures and firing times improved with the addition of barium aluminate in the formulation. Comparison of batches "E” versus “F” and “G” versus “H” demonstrate the trend for strength improvement.
- the invention was further tested by having supports made by a commercial manufacturer of catalyst support materials.
- Four different formulations numbered 1, 2, 3 and 4 were made up both with (A) and without (B) the addition of barium aluminate.
- the material was made into 3/16" diameter spheres and fired at temperatures and for times normally employed in their manufacturing operations.
- Table V shows the physical properties of the support spheres resulting from these experiments.
- the abrasion loss was determined in the manner previously described except that the test container was larger in both length and diameter in order to contain a larger amount of catalyst. This test was conducted for 1 hour instead of a 1/2 hour.
- Each of the formulations were made with high purity alpha alumina which contains about 99.0 weight percent Al 2 O 3 and minor amount of silica (SiO 2 ) and other metal oxides. Various additives to affect the pore size were employed. These catalyst supports were then used as carriers for silver in an ethylene oxide manufacturing process.
- Samples of the modified supports were prepared as silver catalysts by the process of U.S. Pat. No. 4,248,741 for the purpose of testing in a small reactor. A volume of fifty cubic centimeters each of these several catalysts was tested in a one-half inch quartz glass tube reactor at a temperature sufficient to cause thirty percent of the ethylene fed to be converted to reaction products. An ethylene oxide selectivity based on ethylene converted was calculated.
- the feed gas had the following % composition by volume
- barium containing supports as in Example 4 had additional barium incorporated with the silver coating.
- the barium was added as the nitrate along with silver nitrate.
- the results of using these for oxidation of ethylene to ethylene oxide is shown in Table VII.
- the amount of silver loading was the same as in Example 4. All runs were made at 30% conversion.
- the A samples had barium aluminate and the S samples had the barium silicate incorporated into the support during manufacture as in Example 4.
- Example 7 The supports of Example 7 were employed as silver catalysts (18% Ag) in the preparation of EO using a feed gas containing 6.0 mole % C 2 H 4 , 6.2 mole % O 2 , and 7-15 ppb equivalent Cl in EDC as an inhibitor.
- a volume of the catalyst was loaded into a testing reactor having a 11/2 inch diameter reaction tube twenty feet in length.
- a preheater brought the synthetic feed mixture to a temperature of 220° C. before entering the reactor.
- the reaction pressure was 250 psig.
- Each catalyst was run at a temperature sufficient to cause 1.55 mole percent ethylene to be converted to reaction products. This results in about 25.8% conversion of the ethylene. Results are shown in Table X.
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Abstract
Description
TABLE I ______________________________________ Ba Alumina M.C.* Cell.** Aluminate H.sub.2 O Batch (g) (g) (g) (g) (g) ______________________________________ A 98.0 2.0 -- -- 30 B 97.3 2.0 -- 0.7 30 C 88.0 2.0 10.0 -- 8 D 87.3 2.0 10.0 0.7 8 ______________________________________ *Hydroxypropylmethylcellulose (Methocel ® 60 HG 50 cps @ 20° C.), a product of The Dow Chemical Company. **Cellulose, a microcrystalline variety (Avicel ® PH 102) available from FMC Corp.
TABLE II ______________________________________ Median Apparent Pore Crush Batch Porosity Size Strength Attrition I.D. (%) (μ) (lb) (Wt %) ______________________________________ A 45 1.9 87 5.2 B 42 2.2 146 4.0 C 48 5.6 14 -- D 49 5.6 39 -- N 50 8-10 30-40 2.0 ______________________________________
TABLE III ______________________________________ Ba Alumina M.C.* Graphite** Aluminate Batch (g) (g) (g) (g) ______________________________________ E 1000 22.5 -- -- F 1000 22.6 -- 7.2 G 1000 36.6 182.9 -- H 1000 36.9 184.5 8.6 ______________________________________ *Same cellulose material used in Example 1 above. **Grade 7101 graphite available from Asbury Graphite Mills, Inc.
TABLE IV ______________________________________ Median Total Firing Pore Pore Crush Batch Conditions Diameter Volume Strength I.D. (°C./Hr) (μ) (cc/g) (lb) ______________________________________ E 1500/1 2.2 0.199 45.5 1400/1 -- -- 40.0 1500/10 2.5 0.199 59.1 1500/5 2.7 0.211 50.2 F 1500/1 2.9 0.206 49.4 1400/1 -- -- 45.3 1500/10 3.0 0.210 64.9 1500/5 -- -- 62.8 G 1550/1 5.7 0.270 22.6 1550/10 -- -- 28.0 1500/10 5.9 0.299 20.6 1500/5 -- -- 18.4 1500/1 7.6 0.274 14.2 H 1550/1 5.6 0.280 28.8 1550/10 -- -- 37.6 1500/10 5.2 0.243 25.1 1500/5 -- -- 23.8 1500/1 6.2 0.310 14.8 ______________________________________
TABLE V ______________________________________ Sample No. 1A 1B 2A 2B 3A 3B 4A 4B ______________________________________ Surface 0.174 0.284 0.260 0.211 0.225 0.229 0.258 0.192 area - m.sup.2 /g Pore 0.385 0.458 0.388 0.467 0.360 0.309 0.342 0.440 Volume, cc Hg/g Median 14.0 7.0 10.7 7.4 9.3 6.9 11.3 9.0 Pore Diam. μ Crush, 52.0 21.3 36.5 26.9 63.9 63.1 46.9 37.8 FPCS*, Lbs. Abrasion, 2.4 15.8 4.4 11.6 2.2 10.4 2.8 12.8 % loss % Pore Distrib. 1-10μ 37.9 75.3 43.5 73.0 50.9 84.2 42.1 61.2 1-20μ 68.0 89.1 76.4 88.7 83.9 90.9 74.8 90.4 ______________________________________ *FPCS -- flat plate crush strength
TABLE VI ______________________________________ Temperature Selectivity Formulation % Ba (°C.) to EO (%) ______________________________________ 1N 0 266 68.9 1A 0.6 272 75.3 1S 0.6 270 78.0 2N 0 264 75.8 2A 0.6 264 77.5 2S 0.6 259 78.0 3N 0 260 76.2 3A 0.6 258 78.5 3S 0.6 263 78.9 4N 0 263 75.5 4A 0.6 258 75.5 4S 0.6 266 78.2 ______________________________________
TABLE VII ______________________________________ Formulation % Ba Added Temp. (°C.) Select. (%) ______________________________________ 1A 0 272 75.3 1A 0.10 279 74.1 1S 0 270 78.0 1S 0.10 269 77.8 2A 0 264 77.5 2A 0.10 259 77.6 2S 0 259 78.0 2S 0.10 266 78.5 3A 0 258 78.5 3A 0.10 265 77.1 3S 0 263 78.9 3S 0.10 268 77.4 4A 0 258 75.5 4A 0.10 270 75.0 4S 0 266 78.2 4S 0.10 273 77.8 ______________________________________
TABLE VIII ______________________________________ Sample No. 1S 1B 2S 2B 3S 3B 4S 4B ______________________________________ Surface 0.194 0.284 0.244 0.211 0.246 0.229 0.203 0.192 area m.sup.2 /g Pore 0.417 0.458 0.409 0.467 0.410 0.309 0.397 0.440 Volume, cc Hg/g Median 12.9 7.0 11.9 7.4 13.2 6.9 11.5 9.0 Pore Diam. μ Crush, 77.4 21.3 67.9 26.9 69.8 63.1 83.0 37.8 FPCS*, Lbs. Abrasion, 2.6 15.8 4.2 11.6 2.6 10.4 2.8 12.8 % loss % Pore Distrib. 1-10μ 41.6 75.3 47.4 73.0 39.4 84.2 40.2 61.2 1-20μ 84.9 89.1 84.6 88.7 72.5 90.9 69.1 90.4 ______________________________________ *FPCS -- flat plate crush strength
TABLE IX ______________________________________ Sample No. 3A 5A 6A 7A 8A ______________________________________ % Ba 1.0 0.7 0.4 0.7 0.4 Aluminate Added Surface 0.234 0.240 0.251 0.192 0.156 area, m.sup.2 /g Pore 0.340 0.347 0.351 0.386 0.346 Volume, cc Hg/g Median 7.0 6.3 5.6 11.8 12.2 Pore Diam., μ Crush, 60.6 67.8 61.0 77.0 72.9 FPCS*, lbs. Abrasion, 5.0 4.4 5.0 3.0 2.2 % loss % Pore Distrib. 1-10μ 71.5 74.3 75.8 41.5 41.2 1-20μ 84.4 89.4 86.0 79.5 75.4 ______________________________________ *FPCS -- flat plate crush strength
TABLE X ______________________________________ % Ba Aluminate Formulation Added Temperature Selectivity ______________________________________ 3A 1.0 253° C. 69.6 5A 0.7 256° C. 71.2 7A 0.7 256° C. 73.9 8A 0.4 258° C. 73.0 ______________________________________
Claims (13)
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
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US06/395,560 US4428863A (en) | 1982-07-06 | 1982-07-06 | Alumina compositions of improved strength useful as catalyst supports |
CA000446119A CA1211426A (en) | 1982-07-06 | 1984-01-26 | Alumina compositions of improved strength useful as catalyst supports |
DE8484100865T DE3471010D1 (en) | 1982-07-06 | 1984-01-27 | Alumina catalyst supports containing barium salts. |
EP84100865A EP0150238B1 (en) | 1982-07-06 | 1984-01-27 | Alumina catalyst supports containing barium salts |
BR8400434A BR8400434A (en) | 1982-07-06 | 1984-01-30 | ALUMINUM SUPPORTS FOR CATALYSTS, CONTAINING BARIO SALTS. |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
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US06/395,560 US4428863A (en) | 1982-07-06 | 1982-07-06 | Alumina compositions of improved strength useful as catalyst supports |
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US4428863A true US4428863A (en) | 1984-01-31 |
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US06/395,560 Expired - Lifetime US4428863A (en) | 1982-07-06 | 1982-07-06 | Alumina compositions of improved strength useful as catalyst supports |
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US (1) | US4428863A (en) |
EP (1) | EP0150238B1 (en) |
BR (1) | BR8400434A (en) |
CA (1) | CA1211426A (en) |
DE (1) | DE3471010D1 (en) |
Cited By (30)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0196768A1 (en) * | 1985-03-18 | 1986-10-08 | Corning Glass Works | Preparation of monolithic catalyst supports having an integrated high surface area phase |
EP0250688A1 (en) * | 1985-04-17 | 1988-01-07 | The Dow Chemical Company | Polymerization of cyclic dihalophosphazene oligomers |
US5096871A (en) * | 1990-07-03 | 1992-03-17 | Alcan International Limited | Alumina-alkali metal aluminum silicate agglomerate acid adsorbents |
US5145824A (en) * | 1991-01-22 | 1992-09-08 | Shell Oil Company | Ethylene oxide catalyst |
EP0624397A1 (en) * | 1993-05-11 | 1994-11-17 | Exxon Research And Engineering Company | Structurally modified alumina supports and catalysts therefrom |
WO1996023585A1 (en) * | 1995-02-01 | 1996-08-08 | Shell Internationale Research Maatschappij B.V. | Alkylene oxide catalyst and process |
WO1997040933A1 (en) * | 1996-04-30 | 1997-11-06 | Shell Internationale Research Maatschappij B.V. | Epoxidation catalyst and process |
US20040049061A1 (en) * | 2002-06-28 | 2004-03-11 | Lockemeyer John Robert | Method for improving the selectivity of a catalyst and a process for the epoxidation of an olefin |
WO2005023418A1 (en) * | 2003-08-22 | 2005-03-17 | Union Carbide Chemicals & Plastics Technology Corporation | Improved alumina carriers and silver-based catalysts for the production of alkylene oxides |
US20050239644A1 (en) * | 2002-07-12 | 2005-10-27 | Tsinghua University | Method of making photocatalysts by loading titanuim dioxide film on flexible substrates |
US20060014971A1 (en) * | 2004-06-18 | 2006-01-19 | Yeates Randall C | Process for the production of an olefin oxide, a 1, 2-diol, a 1,2-diol ether, or an alkanolamine |
US20060047130A1 (en) * | 2004-09-01 | 2006-03-02 | Shell Oil Company | Olefin epoxidation process, a catalyst for use in the process, a carrier for use in preparing the catalyst, and a process for preparing the carrier |
US20060205962A1 (en) * | 2005-02-21 | 2006-09-14 | Rubinstein Leonid Isaakovich | Olefin epoxidation process, a catalyst for use in the process, a carrier for use in making the catalyst, and a process for making the carrier |
WO2006133183A2 (en) * | 2005-06-07 | 2006-12-14 | Shell Internationale Research Maatschappij B.V. | A catalyst, a process for preparing the catalyst, and a process for the production of an olefin oxide, a 1,2-diol, a 1,2-diol ether, or an alkanolamine |
US20060293180A1 (en) * | 2003-08-22 | 2006-12-28 | Thorsteinson Erlind M | Modified alumina carriers and silver-based catalysts for the production of alkylene oxides |
US20070037704A1 (en) * | 2005-08-10 | 2007-02-15 | Sd Lizenzverwertungsgesellschaft Mbh & Co. Kg | Process for preparation of a catalyst carrier |
US20070111886A1 (en) * | 2003-10-16 | 2007-05-17 | Serafin Juliana G | Catalysts having enhanced stability, efficiency and/or activity for alkylene oxide production |
US20070185339A1 (en) * | 2006-02-03 | 2007-08-09 | Jian Lu | Process for treating a catalyst, the catalyst, and use of the catalyst |
US7479565B2 (en) | 2004-06-18 | 2009-01-20 | Shell Oil Company | Process for the production of an olefin oxide, a 1,2-diol, a 1,2-diol ether, or an alkanolamine |
US20090275764A1 (en) * | 2004-09-01 | 2009-11-05 | Randall Clayton Yeates | Olefin epoxidation process, a catalyst for use in the process, a carrier for use in preparing the catalyst, and a process for preparing the carrier |
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Also Published As
Publication number | Publication date |
---|---|
EP0150238B1 (en) | 1988-05-11 |
BR8400434A (en) | 1985-09-10 |
CA1211426A (en) | 1986-09-16 |
DE3471010D1 (en) | 1988-06-16 |
EP0150238A1 (en) | 1985-08-07 |
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